Binaphthalene derivatives, preparation method thereof and organic electronic device using the same

ABSTRACT

The present invention relates to a new binaphthalene derivative, a preparation method thereof, and an organic electronic device using the same. The binaphthalene derivative according to the present invention can perform functions of hole injection and transportation, electron injection and transportation, or light emission in an organic electronic device including an organic light-emitting device, and the device according to the present invention has excellent characteristics in terms of efficiency, drive voltage and stability, and in particular excellent effects such as a low voltage and a long life time.

TECHNICAL FIELD

The present invention relates to a new binaphthalene derivative, apreparation method thereof, and an organic electronic device using thesame.

This application claims priority benefits from Korean Patent ApplicationNo. 10-2005-0099873, filed on Oct. 21, 2005, the entire contents ofwhich are fully incorporated herein by reference.

BACKGROUND ART

The term “organic electronic device” as used in the presentspecification refers to a device requiring charge exchange between anelectrode and an organic material, using holes and/or electrons. Theorganic electronic device can be largely classified into two typesaccording to its operational principle as follows: One type is anelectronic device having a configuration in which an exciton is formedin an organic material layer by photons flown from an external lightsource into the device and the exciton is separated into an electron anda hole, the electron and the hole formed are transported to a differentelectrode, respectively and used as a current source (voltage source),and the other type is an electronic device having a configuration inwhich a hole and/or electron are/is injected into an organic materialsemiconductor forming an interface with an electrode by applying avoltage or current to two or more electrodes to allow the device tooperate by means of the injected electron and hole.

Examples of the organic electronic device include an organiclight-emitting device, an organic solar cell, an organic photoconductor(OPC) drum and an organic transistor, which all require a hole-injectingor hole-transporting material, an electron-injecting orelectron-transporting material, or a light-emitting material for drivingthe device. Hereinafter, the organic light-emitting device will bemainly and specifically described, but in the above-mentioned organicelectronic devices, the hole-injecting or hole-transporting material,the electron-injecting or electron-transporting material, or thelight-emitting material functions according to a similar principle.

In general, the term “organic light-emitting phenomenon” refers to aphenomenon in which electric energy is converted to light energy bymeans of an organic material. The organic light-emitting device usingthe organic light-emitting phenomenon has a structure usually comprisingan anode, a cathode and an organic material layer interposedtherebetween. Herein, the organic material layer may be mostly formed ina multilayer structure comprising layers of different materials, forexample, the hole-injecting layer, the hole-transporting layer, thelight-emitting layer, the electron-transporting layer, theelectron-injecting layer and the like, in order to improve efficiencyand stability of the organic light-emitting device. In the organiclight-emitting device having such a structure, when a voltage is appliedbetween two electrodes, holes from the anode and electrons from acathode are injected into the organic material layer, the holes and theelectrons injected are combined together to form excitons. Further, whenthe excitons drop to a ground state, lights are emitted. Such theorganic light-emitting device is known to have characteristics such asself-luminescence, high brightness, high efficiency, low drive voltage,wide viewing angle, high contrast and high-speed response.

The materials used for the organic material layer of the organiclight-emitting device can be classified into a light-emitting materialand a charge-transporting material, for example, a hole-injectingmaterial, a hole-transporting material, an electron-transportingmaterial and an electron-injecting material, according to theirfunctions. Further, the light-emitting material can be divided into ablue, green or red light-emitting material and a yellow or orangelight-emitting material required for giving more natural color,according to a light-emitting color. On the other hand, an efficiency ofa device is lowered owing to maximum luminescence wavelength moved to alonger wavelength due to the interaction between the molecules, thedeterioration of color purity and the reduction in light emittingefficiency when only one material is used for the light-emittingmaterial, and therefore a host/dopant system can be used as thelight-emitting material for the purpose of enhancing the color purityand the light emitting efficiency through energy transfer.

In order to allow the organic light-emitting device to fully exhibit theabove-mentioned excellent characteristics, a material constituting theorganic material layer in the device, for example, a hole-injectingmaterial, a hole-transporting material, a light-emitting material, anelectron-transporting material and an electron-injecting material shouldbe essentially composed of a stable and efficient material. However, thedevelopment of a stable and efficient organic material layer materialfor the organic light-emitting device has not yet been fully realized.Accordingly, the development of new materials is continuously desired.The development of such a material is equally required to theabove-mentioned other organic electronic devices.

DISCLOSURE Technical Problem

The present inventors have synthesized a binaphthalene derivative havinga new structure, and then have found that the compound has effects of alow voltage and a long life time when it acts as a layer for electrontransportation and electron injection in an organic light-emittingdevice, thus completing the present invention. In addition, the presentinventors have found that the compound has effects of emitting blue,green or red light when it acts as a layer for light-emitting in anorganic light-emitting device, thus completing the present invention.

Therefore, it is an object of the present invention to provide a newbinaphthalene derivative and a preparation method thereof. Further, itis another object of the present invention to provide an organicelectronic device using the binaphthalene derivative.

Technical Solution

The present invention provides a binaphthalene derivative represented bythe following formula (1):

wherein R1 and R2 may be the same or different from each other, and areeach respectively selected from the group consisting of a substituted orunsubstituted alkenyl group, a substituted or unsubstituted aryl group,a substituted or unsubstituted heteroaromatic group, and a substitutedor unsubstituted arylamino group, provided that one of R1 and R2 may behydrogen.

Preferable examples of the substituted or unsubstituted alkenyl groupinclude an alkenyl group unsubstituted or substituted by a substitutedor unsubstituted C₆˜C₃₀ aryl group or a substituted or unsubstitutedC₅˜C₃₀ heteroaryl group.

Preferable examples of the substituted or unsubstituted aryl groupinclude a C₆˜C₃₀ aryl group unsubstituted or substituted by at least onegroup selected from the group consisting of a halogen atom, an aminogroup, a nitrile group, a nitro group, an alkylboronate, a C₁˜C₃₀ alkylgroup, a C₂˜C₄₀ alkenyl group, a C₁˜C₄₀ alkoxy group, a C₃˜C₃₀cycloalkyl group, a C₃˜C₃₀ heterocycloalkyl group, a C₆˜C₃₀ aryl group,a C₅˜C₃₀ heteroaryl group and a C₆˜C₃₀ arylamino group.

Preferable examples of the substituted or unsubstituted heteraromaticgroup include a C₅˜C₃₀ heteroaromatic group unsubstituted or substitutedby at least one group selected from the group consisting of a halogenatom, an amino group, a nitrile group, a nitro group, an alkylboronate,a C₁˜C₃₀ alkyl group, a C₂˜C₄₀ alkenyl group, a C₁˜C₄₀ alkoxy group, aC₃˜C₃₀ cycloalkyl group, a C₃˜C₃₀ heterocycloalkyl group, a C₆˜C₃₀ arylgroup, a C₅˜C₃₀ heteroaryl group and a C₆˜C₃₀ arylamino group.

Preferable examples of the substituted or unsubstituted arylamino groupinclude a C₆˜C₃₀ arylamino group unsubstituted or substituted by atleast one group selected from the group consisting of a halogen atom, anamino group, a nitrile group, a nitro group, an alkylboronate, a C₁˜C₃₀alkyl group, a C₂˜C₄₀ alkenyl group, a C₁˜C₄₀ alkoxy group, a C₃˜C₃₀cycloalkyl group, a C₃˜C₃₀ heterocycloalkyl group, a C₆˜C₃₀ aryl group,a C₅˜C₃₀ heteroaryl group and a C₆˜C₃₀ arylamino group.

Preferably, in the formula 1, R1 and R2 may be selected from the groupconsisting of the following structural formulas, but not limitedthereto.

In the above structural formulas, X, X₁, X₂ and X₃ may be eachrespectively the same or different from each other, and are eachselected from the group consisting of hydrogen, a substituted orunsubstituted alkyl group, a substituted or unsubstituted alkoxy group,a substituted or unsubstituted alkenyl group, a substituted orunsubstituted aryl group, a substituted or unsubstituted arylaminegroup, a substituted or unsubstituted heterocyclic group, a substitutedor unsubstituted alicyclic group, a substituted or unsubstitutedsilicone group, a substituted or unsubstituted boron group, asubstituted or unsubstituted amino group, a nitrile group, a nitrogroup, a halogen group, a substituted or unsubstituted amide group, anda substituted or unsubstituted ester group, and these may form analiphatic, aromatic, or heterocyclic fused ring, together with theadjacent group.

The alkyl group preferably has 1 to 30 carbon atoms and does not givesteric hindrance. Specific examples thereof include, but not limitedthereto, a methyl group, an ethyl group, a propyl group, an isopropylgroup, a butyl group, a t-butyl group, a pentyl group, a hexyl group anda heptyl group.

Examples of the alkoxy group include an alkoxy group having 1 to 30carbon atoms.

Examples of the alkenyl group include an alkenyl group linked with anaryl group such as a stylbenyl group and a styrenyl group.

Examples of the aryl group include those selected from the groupconsisting of a phenyl group, a naphthyl group, an anthracenyl group, abiphenyl group, a pyrenyl group and a perylenyl group.

Examples of the arylamine group include those selected from the groupconsisting of a diphenylamine group, a phenylnaphthylamine group, aditolylamine group, a phenyltolylamine group, a carbazolyl group and atriphenylamine group.

Examples of the heterocyclic group include those selected from the groupconsisting of a pyridyl group, a bipyridyl group, an acridinyl group, athiophene group, an imidazolyl group, an oxazolyl group, a thiazolylgroup and a quinolyl group.

The alicyclic group preferably has 3 to 30 carbon atoms and does notgive steric hindrance. More preferable specific examples thereofinclude, but not limited thereto, a cyclopentyl group or a cyclohexylgroup.

Examples of the halogen group include fluorine, chlorine, bromine andiodine.

The term “unsubstituted,” in the explanation regarding groups describedin this specification, means that hydrogen is bonded to the groups.

Specific examples of the compound of the formula 1 are shown in thefollowing Tables 1 and 2, but the scope of the present invention is notlimited thereto. Table 1 shows specific examples of the compound inwhich R1 is hydrogen and R2 is a group selected from the groups definedabove except for hydrogen. Table 2 shows specific examples of thecompound in which R1 and R2 are groups selected from the groups definedabove except for hydrogen.

As described in the following Preparation Examples and Examples of thepresent invention, a variety of derivatives, such as the compoundsshowed at Table 1 and 2, can be synthesized under the presence of a Pdcatalyst. Also, simple intermediates can be synthesized as described inthe following Preparation Examples. In other words, the compoundcontaining the binaphthyl group of the above formula (1) can besynthesized by the method.

TABLE 1 Groups as R2 in the compounds of formula (1) having hydrogen asR1 No. R2 1-1

1-2

1-3

1-4

1-5

1-6

1-7

1-8

1-9

1-10

1-11

1-12

1-13

1-14

1-15

1-16

1-17

1-18

1-19

1-20

1-21

1-22

1-23

1-24

1-25

1-26

1-27

1-28

1-29

1-30

1-31

1-32

1-33

1-34

1-35

1-36

1-37

1-38

1-39

1-40

1-41

1-42

1-43

1-44

1-45

1-46

1-47

1-48

1-49

1-50

1-51

1-52

1-53

1-54

1-55

1-56

1-57

1-58

1-59

1-60

1-61

1-62

1-63

1-64

1-65

1-66

1-67

1-68

1-69

1-70

1-71

1-72

1-73

1-74

1-75

1-76

1-77

1-78

1-79

1-80

1-81

1-82

1-83

1-84

1-85

1-86

1-87

1-88

1-89

1-90

1-91

1-92

1-93

1-94

1-95

1-96

1-97

1-98

1-99

1-100

1-101

1-102

1-103

1-104

1-105

1-106

1-107

1-108

1-109

1-110

1-111

1-112

1-113

1-114

1-115

1-116

1-117

1-118

1-119

1-120

1-121

1-122

1-123

1-124

1-125

1-126

1-127

1-128

1-129

1-130

1-131

1-132

1-133

1-134

1-135

1-136

1-137

1-138

1-139

1-140

1-141

1-142

1-143

1-144

1-145

1-146

1-147

1-148

1-149

1-150

1-151

1-152

1-153

1-154

1-155

1-156

1-157

1-158

1-159

1-160

1-161

1-162

1-163

1-164

1-165

1-166

1-167

1-168

1-169

1-170

1-171

1-172

1-173

1-174

1-175

1-176

1-177

1-178

1-179

1-180

1-181

1-182

1-183

1-184

1-185

1-186

1-187

1-188

1-189

1-190

1-191

1-192

1-193

1-194

1-195

1-196

1-197

1-198

1-199

1-200

1-201

1-202

1-203

1-204

1-205

1-206

1-207

1-208

1-209

1-210

1-211

1-212

1-213

1-214

1-215

1-216

TABLE 2 Groups as R1 and R2 in the compounds of formula (1) No. R1 R22-1

2-2

2-3

2-4

2-5

2-6

2-7

2-8

2-9

2-10

2-11

2-12

2-13

2-14

2-15

2-16

2-17

2-18

2-19

2-20

2-21

2-22

2-23

2-24

2-25

2-26

2-27

2-28

2-29

2-30

2-31

2-32

2-33

2-34

2-35

2-36

2-37

2-38

2-39

2-40

2-41

2-42

2-43

2-44

2-45

2-46

2-47

2-48

2-49

2-50

2-51

2-52

2-53

2-54

2-55

2-56

2-57

2-58

2-59

2-60

2-61

2-62

2-63

2-64

2-65

2-66

2-67

2-68

2-69

2-70

2-71

2-72

2-73

2-74

Further, the present invention provides a representative method forpreparing a binaphthalene derivative represented by the formula 1, andthe method is represented by Reaction Scheme 1.

In the Reaction Scheme 1, R1 and R2 have the same meaning as defined inthe formula 1.

As shown in the Reaction Scheme 1, the compound (B) can be easilyprepared by reacting trifluoroacetic anhydride and the naphtolderivatives (A) as a starting material under the presence of a base suchpyridine or triethylamine. The compound (C) can be prepared by reactingthe compound (B) and a bispinacolatodiboron reagent.

The compounds of the formula (1) can be prepared by Suzuki couplingreaction between the compound (B) and a naphthalene boron ester compoundor a naphthalene boronic acid compound under the presence of a palladiumcatalyst [II] and a base (for example, an inorganic base such aspotassium carbonate).

In addition, the compounds of the formula (1) can be prepared by Suzukicoupling reaction between a naphthyl boron ester compound (C) and abromonaphthalene derivetive or a trifluoroacetoxynaphthalene derivativeunder the presence of a palladium catalyst [II] and a base (for example,an inorganic base such as potassium carbonate).

The present invention also provides an organic electronic device usingthe binaphthalene derivative of the formula 1.

The organic electronic device of the present invention can be preparedby a usual method and materials for preparing an organic electronicdevice, except that the above-described compounds are used to form anorganic material layer having at least one layer.

Hereinbelow, the organic light-emitting device will be exemplified.

The compound of the formula 1 can be used as an organic material layerin the organic light-emitting device due to its structural specificity.

In one embodiment of the present invention, the organic light-emittingdevice can have a structure comprising a first electrode, a secondelectrode, an organic material layer interposed therebetween, and can beprepared by a usual method and materials for preparing an organicelectronic device, except that the above-described compound according tothe present inventions are used in at least one layer of the organicmaterial layers in the organic light-emitting device.

The organic material layer in the organic light-emitting device of thepresent invention may be a monolayer structure comprising a singlelayer, or a multilayer structure comprising two or more layers includinga light-emitting layer. If the organic material layer in the organiclight-emitting device of the present invention has a multilayerstructure, it can has a structure in which a hole-injecting layer, ahole-transporting layer, a light-emitting layer, electron-transportinglayer, and the like are laminated. However, the structure of the organiclight-emitting device is not limited thereto, and it can further includea fewer number of organic materials layer. In such the multilayerstructure of organic material layer, the compound of the formula 1 canbe contained in a hole-injecting layer, a hole-transporting layer, alight-emitting layer, a hole-injecting/hole-transporting andlight-emitting layer, and a hole-transporting and light-emitting layer,or an electron-transporting and light-emitting layer, anelectron-transporting layer, an electron-injecting andelectron-transporting layer, and the like.

For example, the structure of the organic light-emitting device of thepresent invention can be those as shown FIGS. 1 to 4, but not limitedthereto.

FIG. 1 illustrates a structure of an organic light-emitting device inwhich an anode (102), a light-emitting layer (105) and a cathode (107)are sequentially laminated on a substrate (101). In this structure, thecompound of the formula 1 can be contained in the light-emitting layer(105).

FIG. 2 illustrates a structure of an organic light-emitting device inwhich an anode (102), a hole-injecting/hole-transporting, andlight-emitting layer (105), an electron-transporting layer (106) and acathode (107) are sequentially laminated on a substrate (101). In thisstructure, the compound of the formula 1 can be contained in thehole-injecting/hole-transporting, and light-emitting layer (105) or theelectron-transporting layer (106).

FIG. 3 illustrates a structure of an organic light-emitting device inwhich a substrate (101), an anode (102), a hole-injecting layer (103), ahole-transporting and light-emitting layer (105), anelectron-transporting layer (106) and a cathode (107) are sequentiallylaminated. In this structure, the compound of the formula 1 can becontained in the hole-injecting layer (103), the hole-transporting andlight-emitting layer (105) or the electron-transporting layer (106).

FIG. 4 illustrates a structure of an organic light-emitting device inwhich a substrate (101), an anode (102), a hole-injecting layer (103), ahole-transporting layer (104), an electron-transporting andlight-emitting layer (105) and a cathode (107) are sequentiallylaminated. In this structure, the compound of the formula 1 can becontained in the hole-injecting layer (103), the hole-transporting layer(104) or the electron-transporting and light-emitting layer (105).

For example, the organic light-emitting device according to the presentinvention can be prepared by depositing a metal, a metal oxide havingconductivity, or metal alloys thereof on a substrate to form an anode;forming an organic material layer comprising a hole-injecting layer, ahole-transporting layer, a light-emitting layer and anelectron-transporting layer on the anode; and depositing a material,which can be used as a cathode, thereon, using a PVD (physical vapordeposition) process such as sputtering and e-beam evaporation.Alternatively, an organic light-emitting device can be prepared bydepositing a cathode material, an organic material layer, and an anodematerial on a substrate.

The organic material layer may be of a multilayer structure containing ahole-injecting layer, a hole-transporting layer, a light-emitting layer,an electron-transporting layer, and the like, but not limited thereto,and may be of a monolayer structure. Further, the organic material layercan be produced to have a fewer number of layers, by using a variety ofpolymeric materials, by means of a solvent process rather than a depositprocess, such as spin coating, dip coating, doctor blading, screenprinting, ink jet printing, and heat transfer processes.

The anode material is preferably a material having a large work functionto facilitate hole injection usually to an organic material layer.Specific examples of the anode material which can be used in the presentinvention include metals such as vanadium, chromium, copper, zinc andgold, or an alloy thereof; metal oxides such as zinc oxide, indiumoxide, indium-tin oxide (ITO), and indium zinc oxide (IZO); acombination of a metal and an oxide such as ZnO:Al and SnO₂:Sb;conductive polymers such as poly(3-methylthiophene),poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole andpolyaniline, but not limited thereto.

The cathode material is preferably a material having a small workfunction to facilitate electron injection usually to an organic materiallayer. Specific examples of the cathode material include metals such asmagnesium, calcium, sodium, potassium, titanium, indium, yttrium,lithium, gadolinium, aluminum, silver, tin and lead, or an alloythereof; multilayer structure materials such as LiF/Al and LiO₂/Al, butnot limited thereto.

The hole-injecting material is a material facilitating hole injectionfrom an anode at low voltage. The HOMO (highest occupied molecularorbital) level of the hole-injecting material is preferably locatedbetween the work function of the anode materials and the HOMO level ofits neighboring organic material layer. Specific examples of thehole-injecting material include organic materials of metal porphyrin,oligothiophene and arylamine series, organic materials of hexanitrilehexaazatriphenylene, organic materials of quinacridone series, organicmaterials of perylene series, and conductive polymers of anthraquinone,polyaniline, and polythiophene series, but are not limited thereto.

The hole-transporting material is a material having high hole mobility,which can transfer holes from the anode or the hole-injecting layertoward the light-emitting layer. Specific examples thereof includeorganic materials of arylamine series, conductive polymers and blockcopolymers having both conjugated portions and non-conjugated portions,but are not limited thereto.

The light-emitting material are a material capable of emitting visiblelight by accepting and recombining holes from the hole-transportinglayer and electrons from the electron-transporting layer, preferably amaterial having high quantum efficiency for fluorescence andphosphorescence. Specific examples thereof include 8-hydroxyquinolinealuminum complex (Alq₃); compounds of carbazole series; dimerized styrylcompounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds ofbenzoxazole, benzthiazole and benzimidazole series; polymers ofpoly(p-phenylenevinylene) (PPV) series; spiro compounds; and compoundsof polyfluorene and rubrene series, but are not limited thereto.

The electron-transporting material is suitably a material having highelectron mobility, which can transfer electrons from the cathode to thelight-emitting layer. Specific examples thereof include8-hydroxyquinoline aluminum complex (Alq₃); complexes including Alq₃;organic radical compounds; and hydroxyflavone-metal complexes, but arenot limited thereto.

The organic light-emitting device according to the invention may be of atop emission structure, a bottom emission structure or a top and bottomemission structure according to the materials used.

The compound according to the invention can function in an organicelectronic device including an organic solar cell, an organicphotoconductor and an organic transistor, according to a principlesimilar to that applied to the organic light-emitting device.

Advantageous Effects

The binaphthalene derivative according to the present invention canperform functions of hole injection and transportation, electroninjection and transportation, or light emission in an organic electronicdevice including an organic light-emitting device, and the deviceaccording to the present invention has excellent characteristics interms of efficiency, drive voltage and stability, and in particularexcellent effects such as a low voltage and a long life time.

DESCRIPTION OF DRAWINGS

FIGS. 1 to 4 illustrate the structures of the organic light-emittingdevices applicable to the present invention.

FIGS. 5 to 14 show data to confirm the synthesis of compounds preparedin Examples 1-2, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 2-1 and 2-4.

BEST MODE Mode for Invention

Hereinafter, the present invention will be described in more detail bymeans of Synthesis Examples and Experimental Examples, but the scope ofthe invention is not limited thereto.

PREPARATION EXAMPLE I-1 Preparation of Compound A-1

Naphthyl-2-boronic acid (17.2 g, 100 mmol), 6-bromo-2-naphtol (22.3 g,100 mmol) and sodium carbonate (27.6 g, 200 mmol) were suspended in amixture of tetrahydrofuran (500 mL) and water (100 mL). To thesuspension, tetrakis(triphenylphosphine)palladium [II] (4.6 g, 4 mmol)was added. The resulting mixture was stirred under reflux for about 24hours and then cooled to room temperature. The organic layer wasseparated and the aqueous layer was extracted from tetrahydrofuran. Thecombined organic extract was dried over magnesium sulfate, andconcentrated in vacuum. The residue was purified with THF/EtOH toprepare a compound A-1 (23.5 g , yield 87%): MS [M+H]⁺=271.

PREPARATION EXAMPLE I-2 Preparation of Compound A-2

A compound A-2 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,bromo Spiro compound (26.5 g, 67 mmol) shown in the above reactionscheme was used instead of 6-bromo-2-naphtol, and6-hydroxynaphthyl-2-boronate (18.0 g, 67 mmol) was used instead ofnaphthyl-2-boronic acid. (27.5 g, yield 90%): MS [M+H]⁺=459

PREPARATION EXAMPLE I-3 Preparation of Compound A-3

A compound A-3 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,9-bromo-10-naphthylanthracene compound (19.1 g, 50 mmol) was usedinstead of 6-bromo-2-naphtol, and 6-hydroxynaphthyl-2-boronate (13.5 g,50 mmol) was used instead of naphthyl-2-boronic acid. (20.5 g, yield92%): MS [M+H]⁺=447

PREPARATION EXAMPLE I-4 Preparation of Compound A-4

A compound A-4 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,6-bromo-2-naphtol (4.5 g, 20 mmol) was used, and9,10-dinaphthylanthracenyl-2-boronate compound (11.1 g, 20 mmol) wasused instead of naphthyl-2-boronic acid. (10 g, yield 87%): MS[M+H]⁺=573

PREPARATION EXAMPLE I-5 Preparation of Compound A-5

A compound A-5 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,1-bromopyrene compound (10 g, 35.6 mmol) was used instead of6-bromo-2-naphtol, and 6-hydroxynaphthyl-2-boronate (9.6 g, 35.6 mmol)was used instead of naphthyl-2-boronic acid (9.3 g, yield 76%): MS[M+H]⁺=345

PREPARATION EXAMPLE I-6 Preparation of Compound A-6

[Compound A-6-1]

A compound A-6 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound A-6-1 shown in the above reaction scheme (10.5 g, 20 mmol)was used instead of 6-bromo-2-naphtol, and 6-hydroxynaphthyl-2-boronate(5.4 g, 20 mmol) was used instead of naphthyl-2-boronic acid. (8.0 g,yield 68%): MS [M+H]⁺=589

PREPARATION EXAMPLE I-7 Preparation of Compound A-7

A compound A-7 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,6-bromo-2-naphtol (11.2 g, 50 mmol) was used, and6-hydroxynaphthyl-2-boronate (13.5 g, 50 mmol) was used instead ofnaphthyl-2-boronic acid. (11.2 g, yield 78%): MS [M+H]⁺=287

PREPARATION EXAMPLE II-1 Preparation of Compound B-1

To the compound A-1 prepared in the Preparation Example I-1 (23.5 g, 87mmol), 100 mL of CH₂Cl₂ was added, and then triethylamine (13.3 g, 130.5mmol) and trifluoroacetic acid anhydride (25.8 g, 130.5 mmol) wereslowly added dropwise while stirring the mixture. The resulting mixturewas stirred at room temperature for 2 hours. Water and CH₂Cl₂ were addedto separate the organic layer, and the organic extract was dried overmagnesium sulfate, and concentrated in vacuum. The residue was purifiedwith CH₂Cl₂/EtOH to prepare a compound B-1. (28.7 g, yield 90%): MS[M+H]⁺=403

PREPARATION EXAMPLE II-2 Preparation of Compound B-2

A compound B-2 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound A-2 prepared in the Preparation Example 1-2 (27.5 g, 60mmol) was used instead of the compound A-1 (29.6 g, yield 89%): MS[M+H]⁺=555

PREPARATION EXAMPLE II-3 Preparation of Compound B-3

A compound B-3 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound A-3 prepared in the Preparation Example I-3 (20.5 g, 45.9mmol) was used instead of the compound A-1. (19.7 g, yield 79%): MS[M+H]⁺=543

PREPARATION EXAMPLE II-4 Preparation of Compound B-4

A compound B-4 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound A-4 prepared in the Preparation Example I-4 (10 g, 17.5mmol) was used instead of the compound A-1. (7.83 g, yield 67%): MS[M+H]⁺=669

PREPARATION EXAMPLE II-5 Preparation of Compound B-5

A compound B-5 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound A-5 prepared in the Preparation Example I-5 (12 g, 34.8mmol) was used instead of the compound A-1. (12.1 g, yield 79%): MS[M+H]⁺ 441

PREPARATION EXAMPLE II-6 Preparation of Compound B-6

A compound B-6 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound A-6 prepared in the Preparation Example I-6 (12 g, 20.4mmol) was used instead of the compound A-1. (7.5 g, yield 54%): MS[M+H]⁺=685

PREPARATION EXAMPLE II-7 Preparation of Compound B-7

A compound B-7 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound A-7 prepared in the Preparation Example I-7 (10 g, 35mmol), triethylamine (8.6 g, 84 mmol) and trifluoroacetic acid anhydride(4.5 g, 84 mmol) were used instead of the compound A-1. (2.2 g, yield45%): MS [M+H]⁺=479

PREPARATION EXAMPLE II-8 Preparation of Compound B-8

A solution of diphenylethylene (7.8 g, 43.3 mmol) in 100 mL of CCl₄ wasmaintained at −15° C., and bromine (Br₂, 2.45 mL, 47.6 mmol) was slowlyadded thereto. 10 g of well-dried silica gel was added to the reactant,and then the resultant was stirred at 80° C. for 1 hour. The temperatureof the reactant was lowered to ambient temperature, and the resultantwas purified by column chromatography to prepare a compound B-8 having abromine group introduced (10.7 g, yield 95%).

MS [M+H]⁺=259

PREPARATION EXAMPLE II-9 Preparation of Compound B-9

To 6-bromo-2-naphthoic acid (5.0 g, 20 mmol), 20 mL of thionyl chloride(SOCl₂), and dimethylformaldehyde (DMF, 1 mL) were added, and themixture was stirred under heating for 4 hours. An excessive amount ofthionyl chloride (SOCl₂) was distilled off in vacuum, and then to thereaction mixture, 20 mL of N-methylpyrrolidine (NMP), andN-phenyl-1,2-diaminobenzene (3.7 g, 20 mmol) were added, and the mixturewas stirred at 160° C. for 12 hours. The mixture was cooled to ambienttemperature, and then an excessive amount of water was added thereto toform a solid. The solid was filtered, washed with water and thenethanol, and dried to prepare a compound B-9 (6.2 g, yield 78%).

MS [M+H]⁺=399

PREPARATION EXAMPLE II-10 Preparation of Compound B-10

Bromobenzene (4.24 g, 27 mmol) was diluted by 100 mL of tetrahydrofurananhydride and maintained at −78° C. To the resulting mixture, n-BuLi(2.5M in Hex, 13.0 mL, 32.4 mmol) was added dropwise and then stirredfor 40 minutes. 2,7-dibromofluorene (7.6 g, 22.5 mmol) was added. Thereaction solution was stirred at −78° C. for 4 hours. The temperature ofthe reaction solution was raised to ambient temperature, and the aqueoussolution of 2N HCl was added to the reaction solution and then stirredfor 6 hours. The layer was separated using ethylether and dried overmagnesium anhydride. The separated organic solvent layer was subjectedto reduced pressure in vacuum and purified by column chromatography(SiO₂, EtOAc/Hexane=1/10) to prepare a compound B-10-1 (6.6 g, yield70%).

MS: [M−H2O]⁺=398

The compound B-10-1 (6.6 g, 15.9 mmol) and benzene (100 mL) were mixed,CF₃SO₃H (1.6 mL, 18.4 mmol) was added thereto, and the mixture wasrefluxed at 80° C. for 6 hours. Using an ice-bath, the reaction solutionwas cooled to 0° C. and a saturated aqueous solution of NaHCO₃ was addedthereto. The layer was separated using water and ethylacetate, and theorganic layer was separated and dried over magnesium anhydride. Then,the organic layer was subjected to reduced pressure in vacuum, andrecrystallized with THF/Hexane to prepare a compound B-10 (7.0 g, yield93%).

MS: [M]⁺=476

PREPARATION EXAMPLE II-11 Preparation of Compound B-11

A compound B-11-1 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound B-10 prepared in Preparation Example II-10 (9.5 g, 20 mmol)was used instead of 6-bromo-2-naphtol, and naphthyl-2-boronic acid (3.4g, 20 mmol) was used. (4.5 g, yield 43%): MS [M]⁺=523

A compound B-11-2 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that thecompound B-11-1 (4.5 g, 8.6 mmol) was used instead of 6-bromo-2-naphtol,and 6-hydroxynaphthyl-2-boronate (2.3 g, 8.6 mmol) was used instead ofnaphthyl-2-boronic acid. (4.84 g, yield 96%): MS [M+H]⁺=587

A compound B-11 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound B-11-2 (4.8 g, 8.2 mmol) was used instead of the compoundA-1. (4.3 g, yield 76%): MS [M+H]⁺=683

PREPARATION EXAMPLE II-12 Preparation of Compound B-12

A compound B-12-1 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that6-bromo-2-naphthaldehyde (5.1 g, 21.5 mmol) was used instead of6-bromo-2-naphtol, and 6-hydroxynaphthyl-2-boronate (5.8 g, 21.5 mmol)was used instead of naphthyl-2-boronic acid. (5.3 g, yield 82%): MS[M+H]⁺=299

A compound B-12 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound B-12-1 (5.3 g, 17.8 mmol) was used instead of the compoundA-1. (3.9 g, yield 56%): MS [M+H]⁺=395

PREPARATION EXAMPLE II-13 Preparation of Compound B-13

To the compound B-12-1 of Preparation Example II-12 (6.0 g, 20 mmol),N-phenyl-1,2-diamino benzene (3.7 g, 20 mmol), 30 mL of toluene and 10mL of acetic acid were added and stirred at 150° C. for 12 hours. Themixture was cooled to ambient temperature and an excessive amount ofwater was added thereto to form a solid. The solid was filtered, washedwith water and then ethanol, and dried to prepare a compound B-13-1.(7.2 g, yield 78%): MS [M+H]⁺=463

A compound B-13 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound B-13-1 (6.2 g, 13.4 mmol) was used instead of the compoundA-1. (5.8 g, yield 77%): MS [M+H]⁺=559

PREPARATION EXAMPLE II-14 Preparation of Compound B-14

5,5′-Dibromo-2,2′-dithiophene (5.00 g, 15.4 mmol), phenylboric acid(2.07 g, 17.0 mmol) and sodium carbonate (4.90 g, 46.3 mmol) weresuspended in a mixture of toluene (30 mL) and water (15 mL). To thesuspension, tetrakis(triphenylphosphine)palladium (0.50 g, 0.46 mmol)was added. The resulting mixture was stirred under reflux for about 24hours. The refluxed mixture was cooled to room temperature and extractedusing chloroform. The organic extract was dried over magnesium sulfate,and concentrated in vacuum. The residue was purified by columnchromatography (n-hexane) to prepare a phenylthiophene compound B-14-1(2.80 g, yield 75%).

MS [M+H]⁺=243

To a solution of the compound B-14-1 prepared as the above (2.80 g, 11.6mmol) in a mixture of chloroform (40 mL) and acetic acid (40 mL),N-bromosuccinimide (5.60 g, 2.1 mmol) was added at 0° C. The mixture washeated to 60° C., and stirred at the same temperature for about 1 hour.Thereafter, the mixture was cooled to room temperature, and stirred forabout 24 hours. Then, the mixture was added to an aqueous potassiumhydroxide solution, and the mixture was extracted using chloroform. Theorganic layer was dried over magnesium sulfate and concentrated invacuum. The resultant was recrystallized from ethanol and purified toobtain a compound B-14 (1.83 g, yield 49%).

MS [M+H]⁺=321

PREPARATION EXAMPLE III-1 Preparation of Compound C-1

The compound B-1 prepared in the Preparation Example II-1 (28.7 g, 78mmol), bis(pinacolato)diboron (23.4 g, 92 mmol) and potassium aceticacid (23 g, 234 mmol) were suspended in dioxane (400 mL). To thesuspension, palladium(diphenylphosphinoferrocene)chloride (1.7 g, 2.34mmol) was added. The mixtuer was stirred at 120° C. for about 6 hoursand cooled to room temperature. The mixture was diluted by water (50 mL)and extracted using dichloromethane (3×50 mL). The organic extract wasdried over magnesium sulfate and concentrated in vacuum. The resultantwas washed with ethanol and dried in vacuum to prepare a compound C-1(27.3 g, yield 92%): MS [M+H]⁺=381

PREPARATION EXAMPLE III-2 Preparation of Compound C-2

A compound C-2 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound B-2 prepared in the Preparation Example II-2 (12 g, 21.6mmol) was used instead of the compound B-1. (11.3 g, yield 92%): MS[M+H]⁺=569

PREPARATION EXAMPLE III-3 Preparation of Compound C-3

A compound C-3 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound B-3 prepared in the Preparation Example II-3 (10 g, 18.4mmol) was used instead of the compound B-1. (6.86 g, yield 67%): MS[M+H]⁺=557

PREPARATION EXAMPLE III-4 Preparation of Compound C-4

A compound C-4 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound B-4 prepared in the Preparation Example II-4 (5 g, 7.5mmol) was used instead of the compound B-1. (4.5 g, yield 87%): MS[M+H]⁺=683

PREPARATION EXAMPLE III-5 Preparation of Compound C-5

A compound C-5 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound B-5 prepared in the Preparation Example II-5 (20 g, 45.4mmol) was used instead of the compound B-1. (11.6 g, yield 56%): MS[M+H]⁺=455

PREPARATION EXAMPLE III-6 Preparation of Compound C-6

A compound C-6 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound B-6 prepared in the Preparation Example II-6 (20.5 g, 30mmol) was used instead of the compound B-1. (15.1 g, yield 72%): MS[M+H]⁺=699

PREPARATION EXAMPLE III-7 Preparation of Compound C-7

A compound C-7 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound B-11 prepared in the Preparation Example II-11 (31 g, 45.4mmol) was used instead of the compound B-1. (28.8 g, yield 91%): MS[M]⁺=697

PREPARATION EXAMPLE III-8 Preparation of Compound C-8

6-bromo-2-naphthaldehyde (4.7 g, 20 mmol) was mixed with 100 mL oftoluene, 20 mL of ethylene glycol and p-toluene sulfonic acid (0.2 g,1.2 mmol) and the mixture was stirred under heating for 48 hours. Thereaction mixture was cooled to ambient temperature and the toluenesolvent was distilled off in vacuum under reduced pressure. Ethanol anda small amount of water were added thereto, and thus formed solid wasfiltered and dried to prepare a compound C-8-1 (5.14 g, yield 92%).

MS [M]⁺=279

The compound C-8-1 prepared as the above,2-(6-bromonaphthalene)-1,3-dioxolane (5 g, 17.9 mmol), was dissolved inanhydrous THF (60 mL), and n-BuLi (26.9 mmol, 2.5M in hexane solution,10.7 mL) was added dropwise thereto at −78° C. under nitrogenatmosphere. The mixture was stirred for about 1 hour and trimethylborate(6.2 mL, 53.7 mmol) was added dropwise at −78° C. After about 30minutes, the ice bath was removed and the mixture was stirred at roomtemperature for about 3 hours. 1N HCl (80 ml) was added to the mixtureand the mixture was extracted using ethylacetate. The organic layer wasdried over magnesium sulfate and concentrated in vacuum. A crude productwas slurrified in petroleum ether, suction filtered, and dried toprepare 2-(6-formylnaphthalene)boronic acid compound C-8 (2.07 g, yield57.8%).

PREPARATION EXAMPLE III-9 Preparation of Compound C-9

A compound C-9 was prepared in the same manner as in the method forpreparing the compound C-8 of Preparation Example III-8, except that inthe method for preparing the compound C-8 of Preparation Example III-8,the compound B-8 prepared in the Preparation Example II-8 (10.7 g, 41.3mmol) was used instead of the compound C-8-1. (4.44 g, yield 48%)

PREPARATION EXAMPLE III-10 Preparation of Compound C-10

A compound C-10 was prepared in the same manner as in the method forpreparing the compound C-8 of Preparation Example III-8, except that inthe method for preparing the compound C-8 of Preparation Example III-8,the compound B-14 prepared in the Preparation Example II-14 (18.3 g,56.8 mmol) was used instead of the compound C-8-1 (7.1 g, yield 48.8%).

PREPARATION EXAMPLE III-11 Preparation of Compound C-11

A compound C-11-1 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,6-bromo-2-naphtol (4.4 g, 20 mmol) was used, and the compound C-1 of thePreparation Example III-1 (7.6 g, 20 mmol) was used instead ofnaphthyl-2-boronic acid. (6.1 g, yield 77%): MS [M+H]⁺=397

A compound C-11-2 was prepared in the same manner as in the method forpreparing the compound B-1 of Preparation Example II-1, except that inthe method for preparing the compound B-1 of Preparation Example II-1,the compound C-11-1 (6.1 g, 15.4 mmol) was used instead of the compoundA-1. (6.9 g, yield 91%): MS [M+H]⁺=699

A compound C-11 was prepared in the same manner as in the method forpreparing the compound C-1 of Preparation Example III-1, except that inthe method for preparing the compound C-1 of Preparation Example III-1,the compound C-11-2 (6.0 g, 12.2 mmol) was used instead of the compoundB-1. (3.5 g, yield 56%): MS [M+H]⁺=507

EXAMPLE 1-1 Preparation of Compound 1-17

A compound 1-17 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-1 of the Preparation Example III-1 (1.9 g, 5 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-2 of thePreparation Example II-2 (2.8 g, 5 mmol) was used instead of6-bromo-2-naphtol. (3.0 g, yield 86%): MS [M+H]⁺=695

EXAMPLE 1-2 Preparation of Compound 2-41

A compound 2-41 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-2 of the Preparation Example III-2 (2.8 g, 5 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-9 (2.0 g, 5mmol) was used instead of 6-bromo-2-naphtol. (2.9 g, yield 77%): MS[M+H]⁺=761

FIG. 5 shows the synthesis data of the compound 2-41.

EXAMPLE 1-3 Preparation of Compound 2-43

A compound 2-43 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-2 of the Preparation Example III-2 (2.8 g, 5 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-6 of thePreparation Example II-6 (3.4 g, 5 mmol) was used instead of6-bromo-2-naphtol. (3.4 g, yield 67%): MS [M+H]⁺=1013

EXAMPLE 1-4 Preparation of Compound 1-157

A compound 1-157 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-1 of the Preparation Example III-1 (3.8 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-9 of thePreparation Example II-9 (4.0 g, 10 mmol) was used instead of6-bromo-2-naphtol. (4.0 g, yield 70%): MS [M+H]⁺=573

FIG. 6 shows the synthesis data of the compound 1-157.

EXAMPLE 1-5 Preparation of Compound 1-173

A compound 1-173 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-11 of the Preparation Example II-11 (5.1 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-9 of thePreparation Example II-9 (4.0 g, 10 mmol) was used instead of6-bromo-2-naphtol. (3.4 g, yield 49%): MS [M+H]⁺=699

FIG. 7 shows the synthesis data of the compound 1-173.

EXAMPLE 1-6 Preparation of Compound 1-166

A compound 1-166 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,naphthyl-2-boronic acid (1.7 g, 10 mmol) was used, and the compound B-6of the Preparation Example II-6 (6.5 g, 9.5 mmol) was used instead of6-bromo-2-naphtol. (6.0 g, yield 90%): MS [M+H]⁺=699

FIG. 8 shows the synthesis data of the compound 1-166.

EXAMPLE 1-7 Preparation of Compound 2-44

A compound 2-44 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-5 of the Preparation Example III-5 (4.5 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-9 of thePreparation Example II-9 (4.0 g, 10 mmol) was used instead of6-bromo-2-naphtol. (3.6 g, yield 56%): MS [M+H]⁺=647

FIG. 9 shows the synthesis data of the compound 2-44.

EXAMPLE 1-8 Preparation of Compound 1-70

A compound 1-70 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-1 of the Preparation Example III-1 (3.8 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound 1-70-2 shownin the above reaction scheme (4.9 g, 10 mmol) was used instead of6-bromo-2-naphtol. (4.6 g, yield 72%): MS [M+H]⁺=633

FIG. 10 shows the synthesis data of the compound 1-70.

EXAMPLE 1-9 Preparation of Compound 1-71

A compound 1-71 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-1 of the Preparation Example III-1 (3.8 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound 1-71-2 shownin the above reaction scheme (4.9 g, 10 mmol) was used instead of6-bromo-2-naphtol. (4.2 g, yield 66%): MS [M+H]⁺=633

FIG. 11 shows the synthesis data of the compound 1-71.

EXAMPLE 1-10 Preparation of Compound 1-72

A compound 1-72 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-1 of the Preparation Example III-1 (3.8 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-3 of thePreparation Example II-3 (5.4 g, 10 mmol) was used instead of6-bromo-2-naphtol. (5.0 g, yield 73%): MS [M+H]⁺=683

FIG. 12 shows the synthesis data of the compound 1-72.

EXAMPLE 1-11 Preparation of Compound 1-201

To the compound C-11-2 prepared in the Preparation Exampl III-11 (2.5 g,5.1 mmol), 80 mL of xylene was added, N-phenyl-3-perylenamine (1.7 g,5.0 mmol), Na(O^(t)Bu) (0.97 g, 10 mmol), Pd(OAc)₂[0.01 g, 0.048 mmol]and P(t-Bu)₃ (0.01 g, 0.072 mmol) were added, and the mixture wasstirred under heating at 140° C. for 3 hours. The reaction temperaturewas lowered to ambient temperature and ethanol was added to the mixtureto form a precipitate. The resulting solid was filtered, and dried. Thesolid was dissolved in an excessive amount of THF, and passed through asilica gel layer for purification. THF was removed in vacuum underreduced pressure, and purified with ethylacetate and ethanol to preparea compound 1-201 (2.3 g, yield 64%). MS [M+H]⁺=722

EXAMPLE 2-1 Preparation of Compound 1-18

A compound 1-18 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-1 of the Preparation Example III-1 (3.8 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-10 of thePreparation Example II-10 (2.1 g, 4.4 mmol) was used instead of6-bromo-2-naphtol. (3.5 g, yield 97%): MS [M+H]⁺=823

FIG. 13 shows the synthesis data of the compound 1-18.

EXAMPLE 2-2 Preparation of Compound 2-45

A compound 2-45 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-7 of the Preparation Example III-7 (3.5 g, 5 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-9 of thePreparation Example II-9 (1.9 g, 5 mmol) was used instead of6-bromo-2-naphtol. (2.5 g, yield 56%): MS [M+H]⁺=889

EXAMPLE 2-3 Preparation of Compound 2-47

A compound 2-47 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-3 of the Preparation Example III-3 (5.6 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound 2-47-2 shownin the above reaction scheme (3.2 g, 10 mmol) was used instead of6-bromo-2-naphtol. (3.5 g, yield 56%): MS [M+H]⁺=633

EXAMPLE 2-4 Preparation of Compound 2-8

The compound C-1 of the Preparation Example III-1 (5 g, 12.6 mmol),Pd(OAc)₂ [0.14 g, 0.63 mmol], n-Bu₄NBr (2.03 g, 6.3 mmol), K₂CO₃ (1.74g, 12.6 mmol), dimethylformaldehyde (DMF, 40 mL) and distilled water(H₂O, 10 mL) were mixed, and the mixture was stirred under heating for12 hours. The mixture was cooled to ambient temperature, and thenpurified by column chromatography (THF/n-Hex=1/4) to prepare a compound2-8 (0.6 g, yield 7.4%).

MS [M+H]⁺=639

Tm; 306.5° C.

Tg; 130.9° C.

FIG. 14 shows the synthesis data of the compound 2-8.

EXAMPLE 2-5 Preparation of Compound 2-50

A compound 2-50 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-4 of the Preparation Example III-4 (3.4 g, 5 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-9 of thePreparation Example II-9 (1.9 g, 5 mmol) was used instead of6-bromo-2-naphtol.

(2.5 g, yield 56%): MS [M+H]⁺=875

EXAMPLE 2-6 Preparation of Compound 2-51

A compound 2-51 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-4 of the Preparation Example III-4 (3.4 g, 5 mmol) wasused instead of naphthyl-2-boronic acid, and the compound 2-51-2 shownin the above reaction scheme (2.0 g, 5 mmol) was used instead of6-bromo-2-naphtol.

(2.8 g, yield 67%): MS [M+H]⁺=848

EXAMPLE 2-7 Preparation of Compound 2-9

The compound B-7 prepared in the Preparation Example II-7 (1.2 g, 2.5mmol), 9,10-dinaphthylanthracenyl-2-boronate compound (4.1 g, 7.4 mmol),and sodium carbonate (1.34 g, 9.72 mmol) were suspended in a mixture oftetrahydrofuran (60 mL) and water (10 mL). To the suspension,tetrakis(triphenylphosphine)palladium (0.06 g, 0.05 mmol) was added. Themixture was stirred under reflux for about 24 hours, and then cooled toroom temperature. The organic layer was separated, and the aqueous layerwas extracted using tetrahydrofuran. The combined organic extract wasdried over magnesium sulfate, and concentrated in vacuum. The residuewas purified with THF/EtOH to prepare a compound 2-9 (1.81 g, yield65%): MS [M+H]⁺=1111

EXAMPLE 2-8 Preparation of Compound 2-12

A compound 2-12 was prepared in the same manner as in the method forpreparing the compound A-1 of Preparation Example I-1, except that inthe method for preparing the compound A-1 of Preparation Example I-1,the compound C-3 of the Preparation Example III-3 (5.6 g, 10 mmol) wasused instead of naphthyl-2-boronic acid, and the compound B-3 of thePreparation Example II-3 (5.4 g, 10 mmol) was used instead of6-bromo-2-naphtol. (4.6 g, yield 54%): MS [M+H]⁺=859

EXAMPLE 2-9 Preparation of Compound 2-38

The compound B-7 prepared in the Preparation Example II-7 (1.1 g, 2.30mmol), the compound C-10 prepared in the Preparation Example III-10(1.86 g, 7.29 mmol), and sodium carbonate (1.34 g, 9.72 mmol) weresuspended in a mixture of tetrahydrofuran (60 mL) and water (10 mL). Tothe suspension, tetrakis(triphenylphosphine)palladium (0.06 g, 0.05mmol) was added. The mixture was stirred under reflux for about 24hours, and then cooled to room temperature. The organic layer wasseparated, and the aqueous layer was extracted using tetrahydrofuran.The combined organic extract was dried over magnesium sulfate, andconcentrated in vacuum. The residue was purified with THF/EtOH toprepare a compound 2-38. (0.78 g, yield 44%)

MS [M+H]⁺=735

EXAMPLE 2-10 Preparation of Compound 2-49

The compound B-7 prepared in the Preparation Example II-7 (1.16 g, 2.43mmol), the compound C-9 prepared in the Preparation Example III-9 (1.3g, 5.83 mmol), and sodium carbonate (1.34 g, 9.72 mmol) were suspendedin a mixture of tetrahydrofuran (60 mL) and water (10 mL). To thesuspension, tetrakis(triphenylphosphine)palladium (0.06 g, 0.05 mmol)was added. The mixture was stirred under reflux for about 24 hours, andthen cooled to room temperature. The organic layer was separated, andthe aqueous layer was extracted using tetrahydrofuran. The combinedorganic extract was dried over magnesium sulfate, and concentrated invacuum. The residue was purified with THF/EtOH to prepare a compound2-49. (0.9 g, yield 61%):

MS [M+H]⁺=611

EXAMPLE 2-11 Preparation of Compound 2-53

To the compound B-1 prepared in the Preparation Exampl II-1 (3.7 g, 10mmol), 100 mL of xylene was added, N-phenylbenzidine (1.4 g, 4.2 mmol),Na(O^(t)Bu) (0.97 g, 10 mmol), Pd(OAc)₂[0.02 g, 0.096 mmol] and P(t-Bu)₃(0.02 g, 0.144 mmol) were added, and the mixture was stirred underheating at 140° C. for 3 hours. The reaction temperature was lowered toambient temperature and ethanol was added to the mixture to form aprecipitate. The resulting solid was filtered, and dried. The solid wasdissolved in an excessive amount of THF, and passed through a silica gellayer for purification. THF was removed in vacuum under reducedpressure, and purified with ethylacetate and ethanol to prepare acompound 2-53 (5.2 g, yield 62%).

MS [M+H]⁺=841

As described in the Preparation Examples, a variety of intermediates canbe synthesized. In addition, as described in the Examples, a variety ofderivatives as shown in Table 1 and 2 can be prepared under a Pdcatalyst by a variety of combination of the intermediates synthesized asabove.

EXPERIMENTAL EXAMPLE 1

A glass substrate on which a thin film of ITO (indium tin oxide) wascoated to a thickness of 1500 Å was immersed in distilled water having adetergent dissolved therein to wash the substrate with ultrasonic waves.At this time, the detergent was a product commercially available fromFisher Co. and the distilled water was distilled water which had beentwice filtered by using a filter commercially available from MilliporeCo. ITO was washed for 30 minutes, and then washing with ultrasonicwaves was repeated twice for 10 minutes by using distilled water. Afterthe completion of washing with distilled water, washing with ultrasonicwaves was carried out by using solvents such as isopropyl alcohol,acetone and methanol. The resultant product was dried, and thentransported to a plasma washing machine. Using an oxygen plasma, thesubstrate was washed for 5 minutes and then transported to a vacuumdepositing machine.

On the ITO transparent electrode thus prepared, hexanitrilehexaazatriphenylene was coated to thicknesses of 500 Å by thermal vacuumdeposition to form a hole-injecting layer. NPB (400 Å) as ahole-transporting material was vacuum deposited, and then an Alq3compound was vacuum deposited to thicknesses of 300 Å for alight-emitting layer.

The compound 2-41 as prepared in Example 1-2 was vacuum deposited on thelight-emitting layer to thickness of 200 Å to form an electron-injectingand -transporting layer. Lithium fluoride (LiF) and aluminum weresequentially deposited on the electron-injecting and -transporting layerto thicknesses of 12 Å and 2000 Å respectively, to form a cathode.

In the above process, the deposition rate of the organic material wasmaintained at 1 Å/sec, the deposition rate of lithium fluoride wasmaintained at 0.2 Å/sec and the deposition rate of aluminum wasmaintained at 3 to 7 Å/sec.

When a forward electric field of 7.2 V was applied to the organiclight-emitting device as prepared above, green light emission wasobserved with x=0.33 and y=0.55 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 7.9V was applied, green light emission of 3.1 cd/A was observed at acurrent density of 100 mA/cm².

EXPERIMENTAL EXAMPLE 2

On the ITO electrode as prepared as in Experimental Example 1,hexanitrile hexaazatriphenylene (500 Å,4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), Alq₃ (300Å), the compound 1-157 prepared in Example 1-4 (300 Å), lithiumfluoride(LiF) (12 Å) were sequentially coated by thermal vacuumdeposition, to form a hole-injecting layer, a hole-transporting layer, alight-emitting layer, an electron-transporting layer and anelectron-injecting layer in this order. Aluminum was deposited thereonto a thickness of 2000 Å to form a cathode, and then to prepare anorganic light-emitting device.

When a forward electric field of 6.12 V was applied to the organiclight-emitting device as prepared above, green light emission wasobserved with x=0.32 and y=0.58 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 7.4V was applied, green light emission of 2.9 cd/A was observed at acurrent density of 100 mA/cm².

EXPERIMENTAL EXAMPLE 3

On the ITO electrode as prepared as in Experimental Example 1,hexanitrile hexaazatriphenylene (500 Å),4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), Alq₃ (300Å), the compound 1-166 prepared in Example 1-6 (300 Å), lithium fluoride(LiF) (12 Å) were sequentially coated by thermal vacuum deposition, toform a hole-injecting layer, a hole-transporting layer, a light-emittinglayer, an electron-transporting layer and an electron-injecting layer inthis order. Aluminum was deposited thereon to a thickness of 2000 Å toform a cathode, and then to prepare an organic light-emitting device.

When a forward electric field of 7.3 V was applied to the organiclight-emitting device as prepared above, green light emission wasobserved with x=0.33 and y=0.56 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 8.9V was applied, green light emission of 3.3 cd/A was observed at acurrent density of 100 mA/cm².

EXPERIMENTAL EXAMPLE 4

On the ITO electrode as prepared as in Experimental Example 1,hexanitrile hexaazatriphenylene (500 Å),4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), Alq₃ (300Å), the compound 2-8 prepared in Example 2-4 (300 Å), lithium fluoride(LiF) (12 Å) were sequentially coated by thermal vacuum deposition, toform a hole-injecting layer, a hole-transporting layer, a light-emittinglayer, an electron-transporting layer and an electron-injecting layer inthis order. Aluminum was deposited thereon to a thickness of 2000 Å toform a cathode, and then to prepare an organic light-emitting device.

When a forward electric field of 8.9 V was applied to the organiclight-emitting device as prepared above, green light emission wasobserved with x=0.33 and y=0.54 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 10.7V was applied, green light emission of 3.7 cd/A was observed at acurrent density of 100 mA/cm².

EXPERIMENTAL EXAMPLE 5

On the ITO electrode as prepared as in Experimental Example 1,hexanitrile hexaazatriphenylene (500 Å),4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), Alq₃ (300Å), the compound 2-44 prepared in Example 1-7 (300 Å), lithium fluoride(LiF) (12 Å) were sequentially coated by thermal vacuum deposition, toform a hole-injecting layer, a hole-transporting layer, a light-emittinglayer, an electron-transporting layer and an electron-injecting layer inthis order. Aluminum was deposited thereon to a thickness of 2000 Å toform a cathode, and then to prepare an organic light-emitting device.

When a forward electric field of 7.1 V was applied to the organiclight-emitting device as prepared above, green light emission wasobserved with x=0.31 and y=0.54 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 8.6V was applied, green light emission of 3.5 cd/A was observed at acurrent density of 100 mA/cm².

EXPERIMENTAL EXAMPLE 6

On the ITO electrode as prepared as in Experimental Example 1,hexanitrile hexaazatriphenylene (500 Å),4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), thecompound 1-71 prepared in Example 1-9 (300 Å), Alq₃ (300 Å), lithiumfluoride (LiF) (12 Å) were sequentially coated by thermal vacuumdeposition, to form a hole-injecting layer, a hole-transporting layer, alight-emitting layer, an electron-transporting layer and anelectron-injecting layer in this order. Aluminum was deposited thereonto a thickness of 2000 Å to form a cathode, and then to prepare anorganic light-emitting device.

When a forward electric field of 7.9 V was applied to the organiclight-emitting device as prepared above, blue light emission wasobserved with x=0.137 and y=0.281 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 9.6V was applied, blue light emission of 2.6 cd/A was observed at a currentdensity of 100 mA/cm².

EXPERIMENTAL EXAMPLE 7

On the ITO electrode as prepared as in Experimental Example 1,hexanitrile hexaazatriphenylene (500 Å), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (400 Å), the compound 1-72prepared in Example 1-10 (300 Å), Alq₃ (300 Å), lithium fluoride (LiF)(12 Å) were sequentially coated by thermal vacuum deposition, to form ahole-injecting layer, a hole-transporting layer, a light-emitting layer,an electron-transporting layer and an electron-injecting layer in thisorder. Aluminum was deposited thereon to a thickness of 2000 Å to form acathode, and then to prepare an organic light-emitting device.

When a forward electric field of 6.7 V was applied to the organiclight-emitting device as prepared above, blue light emission wasobserved with x=0.136 and y=0.154 based on the 1931 CIE color coordinateat a current density of 50 mA/cm². When a forward electric field of 7.9V was applied, blue light emission of 2.9 cd/A was observed at a currentdensity of 100 mA/cm².

The invention claimed is:
 1. A binaphthalene compound represented by thefollowing formula (1):

wherein R1 is selected from the group consisting of hydrogen; a fluorenegroup which is substituted with an aryl group; a naphthyl group; apyrene group; and a heteroaromatic group which is substituted with anaryl group, and R2 is selected from the group consisting of aheteroaromatic group which is substituted with an aryl group and anaphthyl group which is substituted with a heteroaromatic group.
 2. Abinaphthalene compound represented by the following formula (1):

wherein R1 or R2 in the formula (1) is selected from the followingformulas:

in the above structural formulas, X, X₂ and X₃ may be each respectiveltthe same or different from each other, and are each selected from thegroup consisting of hydrogen; an alkenyl group; an alkenyl group whichis substituted with an aryl group; an aryl group; an aryl group which issubstituted with an alkenyl group, an aryl group or a heteroaromaticgroup; a heteroaromatic group; and a heteroaromatic group which issubstituted with an aryl group or a heteroaromatic group, and X1 isselected from the group consisting of an alkenyl group; an alkenyl groupwhich is substituted with an aryl group; an aryl group which issubstituted with an alkenyl group or a heteroaromatic group; aheteroaromatic group; and a heteroaromatic group which is substitutedwith an aryl group or a heteroaromatic group.
 3. A binaphthalenecompound represented by the following formula (1):

wherein, in the formula (1), R1 is hydrogen and R2 is selected from thegroups shown in the following table: No. R2 1-1

1-2

1-3

1-4

1-5

1-6

1-7

1-8

1-9

1-10

1-11

1-12

1-13

1-14

1-15

1-16

1-17

1-18

1-19

1-20

1-21

1-22

1-23

1-24

1-25

1-26

1-27

1-28

1-29

1-30

1-31

1-32

1-33

1-34

1-35

1-36

1-37

1-38

1-39

1-40

1-41

1-42

1-43

1-44

1-45

1-46

1-47

1-48

1-49

1-50

1-51

1-52

1-53

1-54

1-55

1-56

1-57

1-58

1-59

1-60

1-61

1-62

1-63

1-64

1-65

1-66

1-67

1-68

1-69

1-70

1-71

1-72

1-73

1-74

1-75

1-76

1-77

1-78

1-79

1-80

1-81

1-82

1-83

1-84

1-85

1-86

1-87

1-88

1-89

1-90

1-91

1-92

1-93

1-94

1-95

1-96

1-97

1-98

1-99

1-100

1-101

1-102

1-103

1-104

1-105

1-106

1-107

1-108

1-109

1-110

1-111

1-112

1-113

1-114

1-115

1-116

1-117

1-118

1-119

1-120

1-121

1-122

1-123

1-124

1-125

1-126

1-127

1-128

1-129

1-130

1-131

1-132

1-133

1-134

1-135

1-136

1-137

1-138

1-139

1-140

1-141

1-142

1-143

1-144

1-145

1-146

1-147

1-148

1-149

1-150

1-151

1-152

1-153

1-154

1-155

1-156

1-157

1-158

1-159

1-160

1-161

1-162

1-163

1-164

1-165

1-166

1-167

1-168

1-169

1-170

1-171

1-172

1-173

1-174

1-175

1-176

1-177

1-178

1-179

1-180

1-181

1-182

1-183

1-184

1-185

1-186

1-187

1-188

1-189

1-190

1-191

1-192

1-193

1-194

1-195

1-196

1-197

1-198

1-199

1-200

1-201

1-202

1-203

1-204

1-205

1-206

1-207

1-208

1-209

1-210

1-211

1-212

1-213

1-214

1-215

1-216

.


4. A binaphthalene compound represented by the following formula (1):

wherein, in the formula (1), R1 and R2 are selected from the groupsshown in the following table: No. R1 R2 2-1

2-2

2-3

2-4

2-5

2-6

2-7

2-8

2-14

2-15

2-17

2-19

2-20

2-21

2-22

2-30

2-31

2-32

2-34

2-37

2-38

2-39

2-41

2-44

2-45

2-49

2-55

2-69

2-70

2-71

2-72

2-74

.